CN104105531B - Adopt method and the complete set of equipments of the distillating carbinol of heat recovery - Google Patents
Adopt method and the complete set of equipments of the distillating carbinol of heat recovery Download PDFInfo
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- CN104105531B CN104105531B CN201280067890.7A CN201280067890A CN104105531B CN 104105531 B CN104105531 B CN 104105531B CN 201280067890 A CN201280067890 A CN 201280067890A CN 104105531 B CN104105531 B CN 104105531B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/14—Fractional distillation or use of a fractionation or rectification column
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/001—Processes specially adapted for distillation or rectification of fermented solutions
- B01D3/002—Processes specially adapted for distillation or rectification of fermented solutions by continuous methods
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/007—Energy recuperation; Heat pumps
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/14—Fractional distillation or use of a fractionation or rectification column
- B01D3/143—Fractional distillation or use of a fractionation or rectification column by two or more of a fractionation, separation or rectification step
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
- C07C29/80—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
- C07C31/02—Monohydroxylic acyclic alcohols
- C07C31/04—Methanol
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/10—Greenhouse gas [GHG] capture, material saving, heat recovery or other energy efficient measures, e.g. motor control, characterised by manufacturing processes, e.g. for rolling metal or metal working
Abstract
Present invention provide for the method for refining crude methanol and complete set of equipments, including: the under reduced pressure at least three distillation stage of operated in series, wherein, first distillation stage (200) operates under maximum distillation pressure (p2), the after-fractionating stage (300) operates under medium distillation pressure (p3), operate under minimum distillation pressure (p4) with evaporating the stage (400) eventually, wherein, described first distillation stage and described distillation stage produce the gaseous flow (204 of corresponding distillating carbinol respectively, 304), it is sent to the solution containing methanol in next distillation stage accordingly；Wherein, the gaseous flow (204) of at least one the first distillating carbinol produced in the described first distillation stage, the gaseous flow (304) of produced after-fractionating methanol with in the described after-fractionating stage, is, respectively, used as and heats the described after-fractionating stage and evaporate the thermal source in stage described end.
Description
Technical field
The present invention relates to the method for distillating carbinol and complete set of equipments.
Background technology
It is known that be the side-product (including ethanol, ketone, polyhydric alcohol) containing synthetic reaction for the product (being generally defined as crude carbinol) of complete set of equipments of synthesizing methanol and some gas dissolved (mainly includes H2、CO、CO2、N2And CH4) methanol aqueous solution.
Crude carbinol is distilled to meet the pureness specifications needed for market.Such as, AA level specification requirement methanol concentration is minimum is 99.85% (weight), and requires that ethanol is less than 10ppm (weight).
Known still-process is substantially based on one or more rectifying column.Generally, rectifying column can be isolated light product (such as, gas) and isolate heavier product (such as, aqueous solution) in bottom or end at tower top place.
Widely used first process and relevant complete set of equipments include two towers operated under atmospheric or near atmospheric pressure.More specifically, described process uses pretreater (being called topping tower or prerun tower) and secondary stage distillation column.The purpose of the first tower substantially isolates more volatile component contained in crude carbinol；First tower receives crude carbinol and isolates light component (light fraction) at tower top place and isolate aqueous solution at bottom place；Second tower carries out the distillation of reality, it is thus achieved that: the methanol refining at tower top place；At the substantial amounts of current in bottom place (" back water ")；Effluent (is called Alcohols,fusel), and this effluent mainly contains most of side-products of water, the methanol (constituting about the 1% of total amount) of residual and synthetic reaction.Described Alcohols,fusel has specific calorific value and is often used as fuel.
Each tower includes corresponding tower bottom reboiler, the bottom of this reboiler heating tower and maintain still-process.By low-pressure steam or by the process gas (when available) of suitable thermal level, it is provided that heat.Additionally, each tower requires overhead reflux, i.e. a part for the methanol after distillation is condensed and is reintroduced back to tower top.For this purpose, each tower is equipped with the overhead condenser being typically with water or air.
For complete set of equipments, the described configuration with two towers is simple, but it mainly has the disadvantages that owing to tower bottom reboiler supplying heat and the consumption cooling down water and/or electric energy due to overhead condenser, therefore consumes substantial amounts of energy.Additionally, these towers relevant to production capacity have bigger diameter, therefore, complete set of equipments cost is high.
Specifically, the size of the heat consumption of two tower bottom reboilers is that refining methanol per ton is about 0.8Gcal.The energy consumption that crude carbinol owing to producing 1 ton is necessary is 6-8Gcal, thus the size of the energy consumption of distillation be complete set of equipments total amount consumed 10%.Heat pending within the condenser and the heat exchanged in reboiler are suitable.Such as, in the theoretical case removing described heat only with cooling water, the flow velocity of circulation is significant, i.e. methanol per ton is about 80m3, therefore for suction etc., there is high cost.
Exist and attempt reducing at least partly the known of these defects and be distilled into complete equipment and process.US4210495 describes the process utilizing three rectifying columns, it may be assumed that pretreater or topping tower and two distillation column, and the two distillation column is that about 7 bars to the tower of the middle pressing operation of 8 bars and evaporate tower or ending (bottoming) tower eventually respectively.Topping tower and the whole tower that evaporates substantially operate under atmospheric pressure or slightly higher pressure (such as, 1.5 bar).The overhead vapours of medium pressure column can under atmospheric pressure be condensed by such configuration in the tower bottom reboiler evaporating tower eventually, to reclaim heat.But, topping tower and inter-chamber tower must be heated, although therefore less than the complete set of equipments only with two towers, but its specific consumption remains high.
US4592806 describes the improvement of the described process of three towers, and wherein, the 4th tower processes the effluent of two Alcohols,fusel from two rectifying columns.Such scheme can be recovered at least some of of methanol contained in Alcohols,fusel, and as described above, this Alcohols,fusel accounts for the 1%-1.5% of crude carbinol total amount and therefore can not ignore；But, but such improvement slightly increases yield there is no reduction energy consumption.Specifically, new tower also includes tower bottom reboiler and the overhead condenser of consumption of calorie and cooling water or electric energy respectively.
Above-mentioned configuration is still widely used.Basically, the process of prior art need nonetheless remain for a large amount of energy consumption: methanol per ton is about 0.6GCal to 0.8GCal.All the time there is the motivation reducing described energy consumption, and there is the motivation reducing the heat consumed in the overhead condenser of distillation column.Another problem is rendered as equipment (tower) size being directly proportional to complete set of equipments cost.
Summary of the invention
It is an object of the invention to reduce the consumption of energy, cooling water and/or electric energy in the still-process of crude carbinol.
Such purpose adopts the method for the stream for refining crude methanol to realize, including:
At least three distillation stage that-contact under corresponding decompression (cascade) operates, the described at least three distillation stage at least includes being in and the first distillation stage (200) under maximum distillation pressure (p2), the after-fractionating stage (300) being under medium distillation pressure (p3) and the end being under minimum distillation pressure (p4) evaporates the stage (400)
-wherein, described first distillation stage and described after-fractionating stage produce the gaseous flow (204,304) of at least one corresponding distillating carbinol respectively, and are sent to the solution containing methanol in next distillation stage accordingly；And described end evaporates the gaseous flow that the stage produces at least one distillating carbinol and the solution being mainly made up of water；
-wherein, in the described first distillation stage, the gaseous flow (204) of at least one the first distillating carbinol produced and the gaseous flow (304) of after-fractionating methanol produced by the described after-fractionating stage, be, respectively, used as and at least heat the described after-fractionating stage and evaporate the thermal source in stage described end.
The invention provides at least three distillation pressure rank, be particularly in the first distillation stage under high pressure, this first distillation stage can before the topping for isolating volatile component from crude carbinol processes.Preferably, according to detailed description of the invention, the described first distillation stage operates under rated pressure, and this rated pressure is between 10 bars to 35 bars, and is preferably at least 20 bars.
It should be noted that in the prior art, maximum distillation pressure is less than the value of about 8 bars.The present invention includes: in the distillation stage of operation under elevated pressures (such as, 20 bars or 30 bars), it needs have the other thermal source of high energy level, for instance, the steam of condensation under the pressure of 10 bars or higher.It has been discovered by the applicants that the high pressure distillation stage increases the feasibility of the recuperation of heat in still-process itself, this is the availability of the gaseous flow due to distillating carbinol at high temperature and pressure.Have been found that the recuperation of heat improved compensates the needs exceeding the other heat input of high energy level.
Term " series winding (cascade) " refers to that the solution containing methanol obtained in the distillation stage is distilled further in follow-up phase.The general middle distillation stage produces the stream of at least one distillating carbinol being in gaseous state and for the methanol solution of distillation further in follow-up phase.
The finishing phase that the stage that evaporates eventually is normally so-called.The stage that evaporates eventually generally produces the distillating carbinol being in gaseous state, the main solution being made up of water and the effluent represented by so-called Alcohols,fusel.If it is suitable, it is also possible to extract the effluent of Alcohols,fusel from the middle distillation stage.
In some embodiments, even if present invention preferably employs three phases, the present invention can also include the distillation stage of more than three.
The gaseous flow of term distillating carbinol refers to the stream from still-process, for instance, obtain from the tower top of tower.Such stream is mainly made up of the methanol according to required specification (such as, AA level) with low impurity content.
Preferably, pressure is defined such that, the gaseous flow of described distillating carbinol can supply the corresponding net quantity of heat distilling the stage in the downstream being positioned at series winding.Such as, the net quantity of heat of the stream supply second stage of produced distillating carbinol in the first phase, etc..
Preferably, the gaseous flow of described distillating carbinol is condensed at least in part during heat exchange, it is thus achieved that be in the stream of the distillating carbinol of liquid condition accordingly.Such as, by the mode with the indirect heat exchange of the respective streams of the liquid solution containing methanol to be distilled, the gaseous flow of each distillating carbinol supplies the heat in follow-up distillation stage.It is highly preferred that the gaseous flow condensation of distillating carbinol, liquid solution evaporation simultaneously.Respectively at least partially, preferably completely condensation and evaporation.
Such as, liquid solution obtains from the bottom of distillation column, and heated solution (partly or entirely evaporation) is delivered to the bottom of tower again, thus heating this tower.
Pass through which, it is achieved that the associating of the evaporation step of methanol solution (under distillation pressure rank) and the condensing steps of distillating carbinol (under high pressure rank).
The evaporation of described associating and condensing steps can be implemented in a heat exchanger, for instance, this heat exchanger is bundled tube exchanger or plate heat exchanger, and wherein, distillating carbinol condenses in hot side, and solution evaporates in cold side.This heat exchanger had not only operated the tower bottom reboiler as distillation column but also as the tower top vaporizer of high-pressure tower.One of according to aspects of the present invention, such supply has and another advantage is that, it is not necessary at least some overhead condenser, under the auxiliary of embodiment, this point will be apparent from below.
The method can provide pre-topping to process to remove more volatile component.Described topping step is generally performing under atmospheric pressure (usually 1 bar to 1.5 bars).
In contrast to the prior art, another aspect of the present invention includes increasing described minimum distillation pressure (or ending pressure), and the trend existed in prior art is to maintain alap ending pressure and be generally equal to topping pressure.It is true that by raising topping pressure, there is another advantage of energy aspect, this is owing to having, at the stream of distillating carbinol produced by whole evaporating in the stage, the sufficient temp becoming the thermal source for pre-topping step.
Such as, in some embodiments, topping pressure is substantially equal to atmospheric pressure, and minimum distillation pressure is at least 2 bars and preferred about 5 bar.
In other words, applicant have discovered that, (need to be likely to distillation under ending pressure at minimum with prior art, and it is generally equal to topping pressure) contrary, utilizing the gaseous methanol distilled in finishing phase to come pre-topping stage heat supply, the employing of extra high ending pressure can energy-conservation and optimization hot-fluid.
Preferably, it is not necessary to the method reclaiming heat from the stage that evaporates eventually has pressures below: topping pressure and last ending pressure are about 1.5 bars；High pressure phase is about 18 bars to 20 bars；The middle pressure stage is about 8 bars to 10 bars.
Preferably, also reclaiming hot method from the stage that evaporates eventually adopts pressures below to implement: topping pressure is about 1.5 bars；High pressure phase is about 30 bars；The middle pressure stage is about 20 bars；Minimum pressure (ending) stage is about 5 bars.
It should be noted that, it is considered to the corresponding minimum Dt of heat exchange, evaporation solution temperature etc., may determine that the accurate calculating of pressure from the thermal balance of evaporator/condenser.It is true that pressure also determines that the temperature of the hot-fluid of gaseous methanol, accordingly, it is determined that the condensation temperature of methanol.
According to this embodiment, the heat in maximum pressure stage and the heat in possible topping stage, it is possible to input as the unique heat for still-process.Generally, the topping stage needs low-temperature heat (low thermal level) and is therefore advantageously used in the gaseous state distillating carbinol under high pressure/middle pressure, to heat middle pressure stage or finishing phase.Preferably, the topping stage adopts the heat reclaimed in the embodiment of ending distillation under high pressure provided as outlined above.
Topping stage and the distillation stage of described series winding preferably employ corresponding rectifying column and implement.For each stage, if necessary, then the tower of single tower or multiple parallel connection can be used.Each tower is connected at least one tower bottom reboiler and can also be connected to overhead condenser.Some distillation column may be connected to the reboiler/condensor as single heat exchanger operated at elevated pressures, and this reboiler/condensor performs the function of the tower bottom reboiler for distillation column and the function of the overhead condenser of the tower of farther upstream for contacting.
According to appending claims, the present invention also aims to, for implementing the complete set of equipments of described method.
Some advantages of the present invention are as follows.
The present invention can save substantial amounts of energy, compared with prior art, and the about 0.20Gcal of its methanol that can be per ton, i.e. save about 30%.For producing the complete set of equipments of methanol of 5000t/d, energy-conservation reach about 40Gcal/h, its equal to the complete set of equipments including distillation total energy expenditure 3%.Such energy-conservation production cost that can reduce methanol.The consumption consumption also below prior art cooling down water for condenser.
New method is also advantageous that in financial charges, especially for the large sized complete sets of equipment more than 5000t/d.The production of the methanol owing to distilling is divided at least three rectifying column, and each described three towers have the diameter less than the diameter of the distillation column of the known complete set of equipments adopting one or two pressure hierarchy arrangement.For identical distillation yield, due to less volume and the surface of distillation plate, the weight of Gu Ta and cost are also below prior art.
Another advantage is that and greater compactness of heat exchanger can be adopted to replace air-cooled type overhead condenser.Air-cooled type overhead condenser is generally used for being provided with in the methanol complete set of equipments of cooling water of low availability in different positions.Air-cooled type overhead condenser is bulky, although they do not consume water, but they consume electric energy.Advantageously replacing to the heat exchanger with tube bank, this can by the function integration of condenser and reboiler, and therefore this is advantageous for.
Accompanying drawing explanation
Fig. 1 is the schematic diagram of methanol distilling period according to the embodiment of the present invention.
Fig. 2 is the schematic diagram of the methanol distilling period according to another embodiment of the present invention, wherein, and the reboiler of the heat topping tower that the distillating carbinol obtained from ending tower reclaims.
Detailed description of the invention
Fig. 1 to Fig. 2 illustrates the exemplary arrangement of method according to certain embodiments of the present invention and complete set of equipments.
Under Essential Environment, the stream 103 of crude carbinol is refined through topping in tower 100, isolates volatile component 104 and the first solution 105.Then described solution 105 be distilled to obtain the methanol 412 with required purity grade (such as, AA level).
The distillation of the methanol in the embodiment of Fig. 1 to Fig. 2 includes three pressure ranks in high-pressure tower 200, in medium pressure column 300 and in low pressure (also referred to as ending) tower 400 respectively.
Middle distillation stage in tower 200 and tower 300 produce by the method needed for the corresponding gaseous flow 204 of distillating carbinol of rank (such as, AA), gaseous flow 304.Described stream 204, stream 304 are with in the method with heating tower 300 and tower 400 respectively.Fig. 2 illustrates an embodiment, and wherein, the stream from the distillating carbinol of ending tower 400 can be used to heat topping tower 100.
Therefore, represent from outside unique heat input by heat Q1 and the Q2 in the embodiment of Fig. 1 and by the heat Q2 in the embodiment of Fig. 2.It should be noted that owing to heat Q2 is in maximum temperature, therefore heat Q2 can not be recovered in the method.
Two embodiments now be will be described in further detail.
First embodiment
Scheme shown in Fig. 1 includes topping tower 100, ending tower 400 and distillation column 200, distillation column 300.Distillation column 200, distillation column 300 and distillation column 400 decompression (p2 > p3 > p4) under with operated in series.Topping tower 100 is in 1 time operation of pressure p of normally about 1.5 bars；In this embodiment, the pressure p 4 of tower 400 is substantially equal to topping pressure p 1, i.e. p4 ≈ p1.
In this specification, it does not have consider the pressure drop of what pipeline, valve, accessory etc. brought concentration and distribution.Each tower has rated pressure；The pressure of overhead gas and slightly different from the pressure of the liquid extracted at the bottom of tower, this point it is known to those skilled in the art that.
Topping tower 100 includes tower bottom reboiler 101 and overhead condenser 102.Tower 200, tower 300 and tower 400 include corresponding tower bottom reboiler 201, tower bottom reboiler 301 and tower bottom reboiler 401.Tower 400 also has overhead condenser 402.
Topping tower 100 receives the stream 103 of crude carbinol and isolates the gaseous overhead stream 104 formed by the volatile component lighter than methanol (light fraction) and containing solution 105 at the bottom of the tower of methanol.A part 106 for described solution 105 is heated (preferably at least part evaporation), and is recycled by tower bottom reboiler 101.The remainder 107 of described solution 105 is sent to pump 120, and the stream 203 of methanol solution is delivered to high-pressure tower 200 by pump 120.Except the pressure drop of service to tower 200, stream 203 lies substantially in pressure p 2 times.
A part for overhead streams 104 is condensed and recirculation (as shown in pipeline 110).Remainder 115 is discharged or removes.
Tower 200 isolates the overhead streams 204 of the gaseous methanol in 2 times distillations of pressure p and solution 205 at the bottom of tower.Solution 205 at the bottom of tower be recycled (pipeline 206) bottom to tower 200 in part through reboiler 201, remainder (pipeline 207) is sent to follow-up second tower 300.Stream 207 flows through choke valve 220 or equivalent elements, it is thus achieved that lying substantially in the stream 303 under pressure p 3, stream 303 is to tower 300 feed or follow-up distillation stage feed.
The reboiler 101 of topping tower and the reboiler 201 of high-pressure tower 200 are respectively through with symbol Q1 and the Q2 external heat source heat supply indicated.Described thermal source can adopt the steam of condensation at suitable pressures, if feasible, then can use other thermals source.In some embodiments, thermal source can be process gas.
Methanol solution 303 is distilled in solution 305 at the bottom of the stream 304 and tower of gaseous methanol further.Stream 306 from the liquid solution of the bottom of tower 300 is heated in corresponding reboiler 301, with the bottom of heating tower 300 and maintenance still-process.In equivalent embodiments, stream 306 can also is that a part for stream 305.
At high temperature and pressure, by least part of condensation of the gaseous methanol stream 204 of the tower top from tower 200, described reboiler 301 is heated.Stream 204 is condensed at least in part in the hot side of reboiler 301, it is thus achieved that the stream 209 of condensation methanol；A part for described condensate 209 is recycled in tower 200 (pipeline 210), and remainder (pipeline 211) represents the distillating carbinol exported by the method.
In a substantially similar fashion, stream 304 heating tower 400 of gaseous methanol, thus the solution 406 in heated reboiler 401.More specifically, solution 305 spreads for 4 times in pressure p in valve (or equivalent) 320, thus forming the methanol solution 403 of supply column 400.Such as, stream 304 condenses in reboiler 401, forms liquid flow 309, and a part for liquid flow 309 is recycled in tower 300 (pipeline 310), and a part for liquid flow 309 represents distillating carbinol 311.
Preferably, reboiler evaporates solution 206, solution 306 and solution 406 at least in part.
The stream 404 of another gaseous methanol isolated by ending tower 400；A part 411 for described stream represents that remainder 410 is introduced again into tower 400 by the distillating carbinol that the method exports.Total stream 412 of distillating carbinol flows automatically 211, stream 311 and stream 411.Stream 211 and stream 311 under high pressure can diffuse into choke valve or equivalent (not shown).Tower 400 also produces the stream 420 of mainly water and the effluent 430 of Alcohols,fusel, and this Alcohols,fusel generally comprises centesimal residual methanol.
From figure 1 it appears that about still-process, the input of unique outside heat adopts thermal source Q1 and Q2.It is true that all heats of tower 200 and tower 400 by the gaseous flow 204 of distillating carbinol, the gaseous flow 304 of distillating carbinol condensation and at internal recovering.
Should also be noted that reboiler 301 alsos operate as the overhead condenser of tower 200, this is owing to reboiler 301 condenses at least some of of distillating carbinol 204, forms overhead recycle stream 210.Therefore, reboiler 301 is also known as reboiler/condensor.Similarly, reboiler 401 operates the overhead condenser as tower 300.Preferably, for instance, described reboiler/condensor 301, reboiler/condensor 401 represent evaporation and the condensation (or, vice versa) of distillation 204,304 in tube side of solution 306,406 in shell-side by tube-bundle heat exchanger.In other embodiments, it is possible to use there is the plate heat exchanger of the heat exchanger plate being contained in shell.
Should be appreciated that, the reboiler of heat exchanger 301,401 and the dual-use function of condenser are substantial advantage, because which removes the overhead condenser of prior art, for instance, the overhead condenser of prior art uses water or air, and the bigger consumption of water and/or the electric energy for fan.
Advantageously, according to the heat needed for reboiler 301 and reboiler 401 and temperature level, pressure p 2 and p3 are determined respectively.It is true that distillation pressure determines temperature, and reboiler needs temperature difference (Δ T), and this temperature difference is typically about 10 DEG C.It is therefoie, for example, pressure p 2 is determined so that the temperature several years higher than the boiling point of solution 306 that gaseous flow 204 has.
In some embodiments, it is possible to be the further recuperation of heat (not shown) of at least one from stream 211, stream 311, stream 411.Such as, stream 211 has higher temperature (more than 100 DEG C), and in some embodiments, stream 211 can be used to make solution 203 preheat, to reduce heat supply Q2；Because heat Q2 is the most expensive in energy, therefore this is significant advantage.
Second embodiment
Fig. 2 illustrates that another is preferred embodiment.The parts used the same reference numerals to represent and be equal in Fig. 1.
Described Fig. 2 refers to such embodiment, and wherein, the pressure p 4 in tower 400 is substantially greater than topping pressure p 1.Such as, pressure p 1 is about 1 bar to 1.5 bars, and pressure p 4 is at least 2 bars, it will be preferred that 3 bars are to 5 bars.In this case, the gaseous flow 404 of distillating carbinol obtained from the tower top of ending tower 400 has higher temperature and higher pressure, and (usually 3 bars are to 5 bars, and more than 100 DEG C), and the gaseous flow 404 of this distillating carbinol can as the useful thermal source of the reboiler 101 for topping tower.
In the embodiment of fig. 2, a part 440 for described stream 404 is sent to reboiler 101 and cooled in described reboiler 101, it is preferable that being condensed, meanwhile, remainder 414 is sent to overhead condenser 402.The condensate 415 formed in reboiler 101 merges with the condensate carrying out condenser 402, and formation part is introduced back into the stream of the distillating carbinol of (stream 410) ending tower and part output (stream 411).
Embodiment
Embodiment 1
The stream of crude carbinol has following composition: the methanol CH of 83%3OH, 15% H2O, 1.9% dissolve gas, 0.1% impurity.Assuming that the yield of AA level methanol is 5000t/d.
According to prior art, conventional device includes: be in the topping tower under the pressure of 1.5 bars, be in the pressure of 1.5 bars under ending tower, the distillation column that is at the pressure of 8 bars and the temperature of about 130 DEG C.Under these conditions, it is possible to be calculated as follows: for total energy expenditure of tower bottom reboiler: 0.63Gcal/ton (refers to distillating carbinol per ton)；By the heat that the overhead condenser of the overhead condenser of topping tower and ending tower exchanges: 0.60Gcal/ton.
Referring now to the schematic diagram of Fig. 1, it has following pressure and temperature.
Pressure p 1:1.5 bar in topping tower.
Temperature (stream 105) at the bottom place of tower: 90 DEG C.
Stream 204:19 bar, 63 DEG C.
Flow 205:171 DEG C.
Stream 304:9 bar, 132 DEG C.
Flow 305:144 DEG C.
Pressure in ending tower: 1.5 bars.
Flow 404:70 DEG C.
Result of calculation is shown in following table under these conditions.
Relative to prior art considered above, the methanol that the present invention is per ton in this embodiment can save the energy of about 0.10Gcal (20%).For producing the complete set of equipments of 5000t/d methanol, energy-conservation reach 21Gcal/h, its be equivalent to complete set of equipments (including distillation) total energy expenditure 1.5%.Relative to prior art, this device needs the thermal source under higher thermal level, for instance, the steam of about 11 bars or equivalent, but reduction on the energy consumption compensate for this requirement.
Relative to prior art, the consumption for the cooling water of condenser is also less.In typical situations, the consumption of water is cooled down equal to 46m3/ methanol per ton, compared with prior art, saves 14m3/ methanol (-22%) per ton.
Embodiment 2
Referring now to Fig. 2, except following condition is different from previous embodiment, other conditions adopt the condition identical with previous embodiment,
It can be seen that the distillation steam 404 from ending tower 400 is now in enough thermal levels to add heat-heat exchanger 101 and supply in FIG from outside heat Q1.There is result calculated below under these conditions:
It can be seen that this embodiment can be energy-conservation further.
These embodiments show, advantages of the present invention can be quantized as follows: relative to prior art, the energy for the reboiler of tower saves 35% to 40%；Relative to prior art (if water-cooled), the cooling water for the overhead condenser of tower saves 40% to 45%；Energy consumption for distilling (both being cooled down, further through circulating water) by air cooler reduces about 40% to 45%；Reduce the maximum gauge of rectifying column, therefore, can have bigger single column capacity for identical maximum tower diameter；Decrease the investment cost needed for synergic system (cooling power and water subsystem)；Save the expense of the inside of tower.
Claims (17)
1. for a method for refining crude methanol, including:
-under corresponding decompression, at least three of operated in series distills the stage, the described at least three distillation stage at least includes being in and the first distillation stage (200) under maximum distillation pressure (p2), the after-fractionating stage (300) being under medium distillation pressure (p3) and the end being under minimum distillation pressure (p4) evaporates the stage (400)
-wherein, described first distillation stage and described after-fractionating stage produce the gaseous flow (204,304) of at least one corresponding distillating carbinol respectively and are sent to the solution containing methanol in next distillation stage accordingly；And described end evaporates the gaseous flow that the stage produces at least one distillating carbinol and the solution being mainly made up of water；
-wherein, in the described first distillation stage, the gaseous flow (204) of at least one the first distillating carbinol produced and the gaseous flow (304) of after-fractionating methanol produced by the described after-fractionating stage, be, respectively, used as and at least heat the described after-fractionating stage and evaporate the thermal source in stage described end.
2. method according to claim 1, described maximum distillation pressure is between 10 bars to 35 bars.
3. method according to claim 1, described maximum distillation pressure is at least 20 bars.
4. method according to claim 1, wherein, the gaseous flow of described first distillating carbinol and the gaseous flow of described after-fractionating methanol are supplied respectively to for described after-fractionating stage and the net quantity of heat evaporating the stage described end.
5. method according to claim 1, it is characterized in that, by the indirect heat exchange with the respective streams (306,406) of the solution containing methanol to be distilled, the gaseous flow of described first distillating carbinol and the gaseous flow of described after-fractionating methanol are to described distillation stage heat supply.
6. method according to claim 5, it is characterised in that described solution is evaporated at least in part by the effect of described heat exchange.
7. method according to claim 5, it is characterised in that: during described heat exchange, the gaseous flow of described distillating carbinol is condensed at least in part, it is thus achieved that be in the stream (209,309) of the distillating carbinol of liquid accordingly.
8. method according to claim 7, it is characterised in that: a part (210,310) for the stream of described liquid distillate methanol returns to the corresponding distillation stage, and remainder (211,311) originates from the distillating carbinol of described method.
9. method according to claim 1, including: the pretreatment stage (100) of operation under topping pressure (p1), described pretreatment stage is called the topping stage, wherein, the stream of described crude carbinol is separated into the gaseous flow of at least one volatile component and is sent to the liquid solution in described first distillation stage.
10. method according to claim 9, wherein, described minimum distillation pressure (p4) is significantly more than described topping pressure (p1), and, operation the gaseous flow (440) that described end evaporates in the stage produced distillating carbinol is used for being at least partially heated described pre-topping processing stage under described minimum pressure.
11. method according to claim 10, wherein, the described gaseous flow (440) of produced distillating carbinol is evaporated in the stage under topping pressure by being condensed at least in part with the indirect heat exchange of the solution (106) containing methanol at described end.
12. method according to claim 11, wherein, described solution is evaporated at least in part by the effect of described heat exchange.
13. method according to claim 10, wherein, described topping pressure is substantially equal to atmospheric pressure, and described minimum distillation pressure is at least 2 bars.
14. method according to claim 10, wherein, described minimum distillation pressure is 5 bars.
15. method according to claim 9, including: being respectively at three distillation stages under high pressure, middle pressure and minimum pressure, and include the pre-topping stage, wherein, described topping pressure is 1.5 bars, and
-described minimum distillation pressure is substantially equal to described topping pressure, and described high pressure is 20 bars, medium pressure be 8 bars to 10 bars,
Or
-described minimum distillation pressure is at least 3 bars, and described high pressure is 30 bars, and medium pressure is 15 bars to 20 bars.
16. method according to claim 15, wherein, described minimum distillation pressure is at least 5 bars.
17. method according to claim 15, wherein, described distillation stage and described pre-topping process to be implemented respectively at least one corresponding rectifying column (100,200,300,400).
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP12152185.0A EP2617478A1 (en) | 2012-01-23 | 2012-01-23 | Process and plant for distillation of methanol with heat recuperation |
| EP12152185.0 | 2012-01-23 | ||
| PCT/EP2012/072353 WO2013110368A1 (en) | 2012-01-23 | 2012-11-12 | Process and plant for distillation of methanol with heat recuperation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104105531A CN104105531A (en) | 2014-10-15 |
| CN104105531B true CN104105531B (en) | 2016-06-29 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201280067890.7A Active CN104105531B (en) | 2012-01-23 | 2012-11-12 | Adopt method and the complete set of equipments of the distillating carbinol of heat recovery |
Country Status (12)
| Country | Link |
|---|---|
| US (1) | US10040738B2 (en) |
| EP (2) | EP2617478A1 (en) |
| CN (1) | CN104105531B (en) |
| AU (1) | AU2012367104B2 (en) |
| BR (1) | BR112014018109A8 (en) |
| CA (1) | CA2860895C (en) |
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| RU (1) | RU2611499C2 (en) |
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| DE102015102853A1 (en) * | 2015-02-27 | 2016-09-01 | Infineon Technologies Ag | magnetic field sensor |
| CN107812393A (en) * | 2017-10-27 | 2018-03-20 | 烟台国邦化工机械科技有限公司 | A kind of methanol three-effect rectification system and technique |
| CN108273282B (en) * | 2018-02-28 | 2023-11-10 | 重庆云天化天聚新材料有限公司 | Vapor phase low-order heat recovery system of trioxymethylene synthetic distillation tower and recovery method thereof |
| EP3578538A1 (en) * | 2018-06-08 | 2019-12-11 | Casale Sa | Method of revamping of a plant for distillation of methanol |
| CN109646980B (en) * | 2018-11-13 | 2021-07-27 | 天津大学 | Fusel-free oil dividing wall tower coupled methanol multi-effect rectification energy-saving device and method |
| JP7335338B2 (en) | 2018-12-21 | 2023-08-29 | エントエックス・リミテッド | Methods and products for converting carbon dioxide to one or more small organic compounds |
| EP3932897B1 (en) * | 2020-06-29 | 2024-02-21 | Topsoe A/S | Process and apparatus for distillation of methanol |
| RU2742652C1 (en) * | 2020-08-14 | 2021-02-09 | Общество с ограниченной ответственностью "Флотметанол" | Method for producing methanol on a floating platform |
| CN115089990A (en) * | 2020-12-29 | 2022-09-23 | 内蒙古双欣环保材料股份有限公司 | Device and method for recycling high-temperature wastewater from alcoholysis waste liquid through hot water self-coupling |
| EP4039639A1 (en) | 2021-02-04 | 2022-08-10 | Casale Sa | Process for methanol production |
| CN112973169A (en) * | 2021-02-23 | 2021-06-18 | 陆鹤霄 | Combined type methanol evaporator |
| EP4074684A1 (en) * | 2021-04-16 | 2022-10-19 | Evonik Functional Solutions GmbH | Method for the energy-efficient production of alkali metal ethanolates |
| EP4074685A1 (en) * | 2021-04-16 | 2022-10-19 | Evonik Functional Solutions GmbH | Method for the energy-efficient production of alkali metal ethanolates |
| CN113521785A (en) * | 2021-08-18 | 2021-10-22 | 天津大学 | Thermal coupling methanol rectification method of side line and bulkhead recovery tower |
| EP4197993A1 (en) * | 2021-12-14 | 2023-06-21 | Basf Se | Integrated plant and process for the production of methanol from carbon dioxide and hydrogen |
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- 2012-11-12 AU AU2012367104A patent/AU2012367104B2/en active Active
- 2012-11-12 MY MYPI2014701984A patent/MY167631A/en unknown
- 2012-11-12 BR BR112014018109A patent/BR112014018109A8/en active Search and Examination
- 2012-11-12 US US14/374,173 patent/US10040738B2/en active Active
- 2012-11-12 WO PCT/EP2012/072353 patent/WO2013110368A1/en active Application Filing
- 2012-11-12 MX MX2014008831A patent/MX354386B/en active IP Right Grant
- 2012-11-12 CN CN201280067890.7A patent/CN104105531B/en active Active
- 2012-11-12 EP EP12784590.7A patent/EP2806957B1/en active Active
- 2012-11-12 RU RU2014134399A patent/RU2611499C2/en active
- 2012-11-12 CA CA2860895A patent/CA2860895C/en active Active
- 2012-12-11 UA UAA201409298A patent/UA112341C2/en unknown
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| US4592806A (en) * | 1983-03-29 | 1986-06-03 | Uhde Gmbh | Process for the production of grade AA methanol |
| EP0210888A1 (en) * | 1985-06-28 | 1987-02-04 | Institut Français du Pétrole | Distillation process with energy recuperation by an ejection stream compressor |
| CN102039058A (en) * | 2010-11-26 | 2011-05-04 | 天津大学 | Large-scale methanol multi-effect energy-saving rectifying device and process |
Also Published As
| Publication number | Publication date |
|---|---|
| RU2611499C2 (en) | 2017-02-27 |
| AU2012367104A1 (en) | 2014-09-04 |
| CN104105531A (en) | 2014-10-15 |
| US20150008116A1 (en) | 2015-01-08 |
| RU2014134399A (en) | 2016-03-20 |
| CA2860895C (en) | 2019-09-17 |
| BR112014018109A2 (en) | 2017-06-20 |
| MX354386B (en) | 2018-03-02 |
| CA2860895A1 (en) | 2013-08-01 |
| UA112341C2 (en) | 2016-08-25 |
| CL2014001932A1 (en) | 2015-02-20 |
| AU2012367104B2 (en) | 2017-11-09 |
| US10040738B2 (en) | 2018-08-07 |
| EP2806957A1 (en) | 2014-12-03 |
| EP2617478A1 (en) | 2013-07-24 |
| MY167631A (en) | 2018-09-21 |
| EP2806957B1 (en) | 2016-04-13 |
| MX2014008831A (en) | 2015-07-06 |
| BR112014018109A8 (en) | 2017-07-11 |
| WO2013110368A1 (en) | 2013-08-01 |
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